Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods [[electronic resource] /] / by Gui-Juan Cheng

• Autore: Cheng Gui-Juan
• Pubblicazione: Singapore : , : Springer Singapore : , : Imprint : Springer, , 2017
• Edizione: 1st ed. 2017.
• Descrizione fisica: 1 online resource (XVII, 126 p. 95 illus., 77 illus. in color.)
• Disciplina: 547.2
• Soggetto topico: Chemistry, Physical and theoretical; Organometallic chemistry ; Catalysis; Mass spectrometry; Theoretical and Computational Chemistry; Organometallic Chemistry; Mass Spectrometry
• Note generali: "Doctoral Thesis accepted by Peking University, Beijing, China." -- title page.
• Nota di bibliografia: Includes bibliographical references at the end of each chapters.
• Nota di contenuto: Introduction -- Mechanistic Studies on meta-C-H Activation Reaction -- Mechanistic Studies on MPAA-assisted meta-C-H Activation Reaction -- Mechanistic Studies on MPAA-assisted Asymmetric C-H Activation Reaction -- Mechanistic Studies on Cu-catalyzed sp3 C-H Cross-Dehydrogenative-Coupling Reaction -- Conclusions and Outlook.
• Sommario/riassunto: This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.
• Titolo autorizzato: Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods
• ISBN: 981-10-4521-6
• Formato: Materiale a stampa
• Livello bibliografico: Monografia
• Lingua di pubblicazione: Inglese
• Record Nr.: 9910254152703321
• Lo trovi qui: Univ. Federico II
• Serie: Springer Theses, Recognizing Outstanding Ph.D. Research, . 2190-5053